Journal
CHEMICAL SCIENCE
Volume 3, Issue 8, Pages 2576-2586Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/c2sc20399e
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Funding
- MICINN [CTQ2010-21497, CSD2006-0003]
- Generalitat de Catalunya [CIRIT/2009 SGR 69]
- WCU Program Korea [R31-10010]
- Deutsche Forschungsgemeinschaft [Ha3265/3-1]
- UniCat cluster of excellence (Unifying Concept in Catalysis, Berlin)
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The water-oxidation catalytic activity of [Ru-II(damp)(bpy)(H2O)](2+) has been determined from manometric and mass spectroscopy studies. Mechanistic details of the catalytic cycle have been studied both experimentally and using DFT and CASSCF/CASPT2 calculations. Characterisation of this Ru(II) complex and more highly oxidized catalytic intermediates has been accomplished through UV-vis and XAS spectroscopy, as well as through electrochemical techniques. Comparison of XAS spectra with CASSCF/CASPT2 calculations provides insight into the electronic structures of the more highly oxidized species, especially the degree to which oxidation occurs over both atoms of the Ru-O fragment. O-18-labelling experiments indicate that the O-O bond formation step proceeds via a water nucleophilic attack mechanism, and a detailed DFT analysis of the catalytic cycle predicts that step to be rate-determining and to take place for a formal Ru(V)=O species. A number of alternative higher energy pathways have also been characterised in order to provide a more complete vision of the whole system.
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